EP0087347B1 - Procédé de préparation de benzoxazolone-2 et dérivés à partir d'orthonitrophénols et de monoxyde de carbone - Google Patents

Procédé de préparation de benzoxazolone-2 et dérivés à partir d'orthonitrophénols et de monoxyde de carbone Download PDF

Info

Publication number
EP0087347B1
EP0087347B1 EP83400269A EP83400269A EP0087347B1 EP 0087347 B1 EP0087347 B1 EP 0087347B1 EP 83400269 A EP83400269 A EP 83400269A EP 83400269 A EP83400269 A EP 83400269A EP 0087347 B1 EP0087347 B1 EP 0087347B1
Authority
EP
European Patent Office
Prior art keywords
process according
reaction
solvent
noble metal
benzoxazolone
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP83400269A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0087347A1 (fr
Inventor
Jacques Kervennal
Jean-Marie Cognion
Pierre Durual
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Atochem SA
Elf Atochem SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Atochem SA, Elf Atochem SA filed Critical Atochem SA
Priority to AT83400269T priority Critical patent/ATE17577T1/de
Publication of EP0087347A1 publication Critical patent/EP0087347A1/fr
Application granted granted Critical
Publication of EP0087347B1 publication Critical patent/EP0087347B1/fr
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2

Definitions

  • the present invention relates to a process for the preparation of benzoxazolone-2 and derivatives by reaction, in the presence of a nitrogenous heteroaromatic base, of orthonitrophenols with carbon monoxide under high pressure and in the presence of supported catalysts consisting of a noble metal and of another transition metal deposited in the form of particles or metal oxides.
  • Benzoxazolone-2 is an intermediate used in fine chemistry, especially in the development of certain dyes.
  • the classical synthesis, starting from orthonitrophenol requires two stages, the first, of hydrogenation to orthoaminophenol, the second, of phosgenation.
  • the disadvantages linked to the use of phosgene are multiple: need to synthesize and handle this dangerous product and under-production of significant quantities of hydrochloric acid which must either be engaged in a reaction by consuming, or electrolyzed, which requires the establishment and costly maintenance of an additional workshop.
  • catalytic systems consisting of a noble metal and a second transition metal present in the form of metallic crystallites or oxides deposited on a support, associated with a heteroaromatic nitrogenous base prove to be particularly selective and exhibit a increased activity in the carbonylation of orthonitrophenols to benzoxazolones-2.
  • the process according to the invention is applicable to the orthonitrophenol molecules of formula: in which R represents a hydrogen or halogen atom, an alkyl group containing from 1 to 10 carbon atoms, an alkoxy group OR 'in which R' represents an alkyl group having from 1 to 10 carbon atoms.
  • the technique according to the invention consists in associating on the support a noble metal from group VIII of the periodic table with a second transition metal chosen from groups Vb, Vl b or VIII and present in the form of metallic particles or oxides.
  • pairs which are favorably associated there may be mentioned, without limitation, the following systems: palladium-molybdenum, palladium-iron, palladium-vanadium, platinum-molybdenum, platinum-iron.
  • the metals or oxides can be deposited on different supports, from various mineral or organometallic compounds, according to known techniques of impregnation to lead, after appropriate treatment, to the catalysts used in the invention.
  • the metal compounds can be introduced one after the other but it is preferable to impregnate them together.
  • the support under a nitrogen atmosphere, can be covered with a solution of metallic derivatives in an organic solvent or in water, then the whole is degassed under vacuum and the solvent distilled.
  • the support is placed in a constantly and regularly agitated rotary evaporator flask and the spray is sprayed with a solution of metal derivatives, under temperature and pressure conditions such that the solvent is evaporated as and as it is introduced.
  • the impregnated support is, after drying, brought to at least 300 ° C. under nitrogen using a linear temperature programming, at a rate of 2 ° C./min in order to decompose the precursors into metallic crystallites or active oxides in the reaction studied.
  • the supports that can be used are various; in a nonlimiting manner, mention may be made of aluminas, silicas, silica-aluminas, magnesia, active carbon, silicon carbides.
  • the impregnation can be carried out so as to lead to noble metal contents on the support of 0.1 to 20% by weight and preferably from 1 to 15%.
  • the ratio of the number of gram atoms of the second metal compared to the noble metal varies from 10- 2 to 10 2 to preferably 0.1 to 10.
  • the nitrophenol is brought into contact with carbon monoxide at elevated temperature and pressure in the presence of the catalyst deposited on the support and of pyridine.
  • reaction medium makes it possible to improve the activity and the selectivity of the catalyst. It is added to the reaction medium in amounts ranging from 10- 2 to 30 moles per mole of nitro derivative and preferably 0.1 to 10 moles per mole.
  • the catalyst concentration in the reaction medium expressed as the ratio of the number of gram atoms of noble metal to the number of nitro groups to transform varies from 10- 4 to 1 and preferably from 5.10 3-1 0-1.
  • the reaction can be carried out in the absence of solvent, by working in molten o-nitrophenols, but dilution in a solvent can promote selectivity.
  • the solvents preferably used are saturated or aromatic hydrocarbons such as hexane, heptane, n-decane, decalin, benzene, toluene or xylene, aromatic halides such as chlorobenzene and dichlorobenzenes; or nitrogen heterocycles such as pyridine, bipyridine; fluorinated solvents such as perfluorinated methyldecaline, trichlorotrifluoroethane can also be used.
  • the proportion is not critical, but it is generally working with solutions of 5 to 50% by weight of the nitro derivative in the solvent.
  • the reaction temperatures are between 100 and 500 ° C and more particularly between 150 ° C and 250 ° C.
  • the pressures are between 20 and 500 bars and preferably between 100 and 350 bars.
  • the catalysts Due to their insolubility in the reaction medium, the catalysts are easily recovered after reaction by simple filtration and their stability makes it possible to recycle them without loss of activity.
  • the impregnated and dried support is transferred into a cooking tube swept with nitrogen, the temperature of which is gradually raised at the rate of 2 ° C./min to 300 ° C. After a plateau of 20 hours at this temperature, a stream of hydrogen is passed through for 20 minutes and then cooled under nitrogen.
  • the analysis indicates a content of 4.8% in palladium and 5.8% in molybdenum.
  • TEST A The autoclave of 500 ml in Hastelloy C is loaded with 13.9 g of orthonitrophenol, 2.22 g of the catalyst previously prepared and the total volume is brought to 100 ml with orthodichlorobenzene. After sweeping with nitrogen, carbon monoxide is introduced up to a pressure of 200 bars and the temperature is brought to 200 ° C. After 1 hour of induction, the pressure drops slowly and stabilizes after 5 hours of reaction. After cooling and dry distillation of the reaction mixture, it is analyzed. The T.T.G. is 97% and the gross selectivity to benzoxazolone-2 is 91%.
  • TEST B The Hastelloy C autoclave is loaded with 13.9 g of orthonitrophenol, 2.1 g of 5% palladium catalyst on alumina sold by the company ENGELHARD (the alumina support has a specific surface greater than 100 m 2 / g), 1 g of pyridine, the volume being made up to 100 ml with orthodichlorobenzene.
  • the total pressure is brought to 200 bars at ordinary temperature using carbon monoxide, then heating to 200 ° C. After one hour of induction without consumption, it is left to react for 4 h 30 min. The reaction mixture is then analyzed at the outlet of the reactor.
  • the TTG is 100% and the selectivity to benzoxazolone 89.5%.
  • Example 2 According to the technique described in Example 1, 0.92 g of ammonium molybdate is then successively impregnated onto 10 g of the pure alumina sold by CONDEA CHEMIE, then 0.97 g of palladium acetate. After the heat treatment, a catalyst is recovered, the metered contents of palladium and molybdenum are 3.5% and 4.5% respectively.
  • a mixed catalyst based on palladium and molybdenum is prepared according to the procedure described in Example 1.
  • the respective contents of palladium and molybdenum, indicated by the analysis, are 4.7% and 4.2%.
  • the 2.3 g of the catalyst recovered in the previous example are recycled to the reactor with 13.3 g of orthonitrophenol, 1 g of pyridine and orthodichlorobenzene as solvent (qs 100 ml), so that the total volume or 100 ml.
  • the operation is carried out under the same conditions as in Example 4, with 200 bars of carbon monoxide pressure, and at 200 ° C. It is also left to react for 1 hour 50 minutes, then the content of the reactor is analyzed.
  • the T.T.G. orthonitrophenol is 100% and the selectivity for benzoxazolone-2 is 100%. There is therefore no decrease in activity or selectivity in recycling the catalyst.
  • Example 1 an aqueous solution containing 1.05 g of palladium acetate and 2.07 g of ferric oxalate pentahydrate is impregnated jointly on 10 g of the pure alumina sold by CONDEA CHEMIE. After the heat treatment, a catalyst is obtained, the metered contents of palladium and iron being 4.6% and 4.0% respectively.
  • the cluster is prepared according to the method of P. Braunstein et al., Angew. Chem. lnt. Ed. Engl, 1978, 17, 596 and R. Bender and P. Braunstein, J. Organometallic, chem., 172 (1979) C 51 -C 54 . After heat treatment at 350 ° C., the analysis indicates that the catalyst thus prepared contains 4% of palladium and 1.9% of chromium.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP83400269A 1982-02-23 1983-02-08 Procédé de préparation de benzoxazolone-2 et dérivés à partir d'orthonitrophénols et de monoxyde de carbone Expired EP0087347B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83400269T ATE17577T1 (de) 1982-02-23 1983-02-08 Verfahren zur herstellung von 2-benzoxazolon und seinen derivaten aus orthonitrophenolen und carbonmonoxid.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8202921 1982-02-23
FR8202921A FR2521994A1 (fr) 1982-02-23 1982-02-23 Procede de preparation de benzoxazolone-2 et derives a partir d'orthonitrophenols et de monoxyde de carbone

Publications (2)

Publication Number Publication Date
EP0087347A1 EP0087347A1 (fr) 1983-08-31
EP0087347B1 true EP0087347B1 (fr) 1986-01-22

Family

ID=9271241

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83400269A Expired EP0087347B1 (fr) 1982-02-23 1983-02-08 Procédé de préparation de benzoxazolone-2 et dérivés à partir d'orthonitrophénols et de monoxyde de carbone

Country Status (7)

Country Link
US (1) US4454322A (enrdf_load_stackoverflow)
EP (1) EP0087347B1 (enrdf_load_stackoverflow)
JP (1) JPS58157775A (enrdf_load_stackoverflow)
AT (1) ATE17577T1 (enrdf_load_stackoverflow)
DE (1) DE3361877D1 (enrdf_load_stackoverflow)
FR (1) FR2521994A1 (enrdf_load_stackoverflow)
SU (1) SU1179928A3 (enrdf_load_stackoverflow)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4558136A (en) * 1983-04-22 1985-12-10 Eastman Kodak Company Preparation of 2-benzoxazolinones
US4653879A (en) * 1985-03-01 1987-03-31 Fjw Industries, Inc. Compact see-through night vision goggles
GB8618573D0 (en) * 1986-07-30 1986-09-10 Shell Int Research Preparation of 2-benzoxazolones
US5312952A (en) * 1992-04-23 1994-05-17 Uniroyal Chemical Company, Inc. Polymerization inhibitor for vinyl aromatics
ITUB20152422A1 (it) * 2015-07-23 2017-01-23 Procos Spa Processo per la sintesi di chlorzoxazone

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3523964A (en) * 1967-04-10 1970-08-11 Olin Corp Preparation of aromatic isocyanates
US3657265A (en) * 1968-06-21 1972-04-18 Olin Corp Process for preparing benzoxazolones from aromatic nitro compounds
CH514616A (de) * 1968-10-07 1971-10-31 Ciba Geigy Ag Verfahren zur Herstellung von Arylenoxazolen
US3832401A (en) * 1971-03-04 1974-08-27 Texaco Inc Homogeneous catalysts useful in the reduction of nitroaromatics to amines
JPS4834875A (enrdf_load_stackoverflow) * 1971-09-13 1973-05-22

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 87, no. 16, 17 octobre 1977, page 30, no. 118492m, Columbus, Ohio, USA B.K. NEFEDOV et al.: "Catalytic synthesis of 2,4-tolylene diisocyanate by the carbonylation of 2,4-dinitroteluene by carbon monoxide" *

Also Published As

Publication number Publication date
FR2521994B1 (enrdf_load_stackoverflow) 1984-10-19
JPS58157775A (ja) 1983-09-19
FR2521994A1 (fr) 1983-08-26
DE3361877D1 (en) 1986-03-06
SU1179928A3 (ru) 1985-09-15
EP0087347A1 (fr) 1983-08-31
ATE17577T1 (de) 1986-02-15
US4454322A (en) 1984-06-12

Similar Documents

Publication Publication Date Title
EP2097431B1 (fr) Complexes catalytiques a base de ruthenium et utilisation de tels complexes pour la metathese d'olefines
CA1077061A (fr) Procede d'oxydation de cetones .beta.-ethyleniques
EP0087347B1 (fr) Procédé de préparation de benzoxazolone-2 et dérivés à partir d'orthonitrophénols et de monoxyde de carbone
CA1270489A (fr) Procede pour la fabrication d'oxydes d'amines tertiaires aromatiques et produits ainsi obtenus
FR2784104A1 (fr) Procede de preparation de la vitamine e
EP0506525B1 (fr) Préparation du pentafluoroéthane par hydrogénolyse du chloropentafluoroéthane
EP0648731A1 (fr) Procédé d'hydroxycarbonylation du butadiène
EP0030528B1 (fr) Procédé pour la fixation de groupes alkyles, aralkyles ou cycloalkyles sur une chaîne carbonée portant un groupe fonctionnel
FR2472414A1 (fr) Autre catalyseur pour la deshydrogenation des derives oxygenes de la serie du cyclohexane en cetones cycliques et/ou phenols correspondants et procede de deshydrogenation des derives precites par mise en oeuvre de ce catalyseur
US4255584A (en) Method for preparing 5-cyano-4-methyl-oxazole
CH642373A5 (fr) Compose pyrannique, procede pour sa preparation et son utilisation a titre d'intermediaire de synthese.
FR2658187A1 (fr) Nouveaux acides alpha-hydroxyles, procede de preparation et leur utilisation.
EP0078729B1 (fr) Procédé de fabrication d'isocyanates aromatiques par carbonylation des dérivés nitrés en présence de catalyseurs supportés préparés à partir de complexes hétéropolymétalliques
Vicart et al. Carbopalladation-sulphonylation of allene: A versatile preparation of 2-vinyl or 2-aryl allyl sulphones
EP0398783B1 (fr) Procédé de synthèse de cyanures d'acyle
FR2553761A1 (fr) Procede continu pour la preparation de bisfluoroxydifluoromethane
EP0019517B1 (fr) Procédé de préparation des isocyanates organiques à partir des dérivés nitrés
JPH0673007A (ja) ２−クロロ−５−アミノメチルピリジンの製造法
EP0326455B1 (fr) Procédé de préparation de chloranil
EP0012390B1 (fr) Procédé pour la préparation de la muscone et composés pyranniques intermédiaires
EP0398782A1 (fr) Procédé de préparation de cyanures d'acyles en milieu anhydre
EP0380393B1 (fr) Preparation d'esters d'acide-2 chloropropionique
BE1003167A3 (fr) Procede de synthese du dimethylcarbonate par carbonylation deshydrogenante.
FR2464247A1 (fr) Procede de preparation du chloro-5 nitro-2 phenol
CH655722A5 (fr) Procede de preparation de derives de l'acide 2-thiophene acetique.

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19830211

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: SOCIETE ATOCHEM

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

RIN1 Information on inventor provided before grant (corrected)

Inventor name: DURUAL, PIERRE

Inventor name: COGNION, JEAN-MARIE

Inventor name: KERVENNAL, JACQUES

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

REF Corresponds to:

Ref document number: 17577

Country of ref document: AT

Date of ref document: 19860215

Kind code of ref document: T

ITF It: translation for a ep patent filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19860228

REF Corresponds to:

Ref document number: 3361877

Country of ref document: DE

Date of ref document: 19860306

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: ATOCHEM

NLT2 Nl: modifications (of names), taken from the european patent patent bulletin

Owner name: ATOCHEM TE PUTEAUX, FRANKRIJK.

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19870115

Year of fee payment: 5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Effective date: 19890208

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19910125

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19910208

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19910212

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19910227

Year of fee payment: 9

ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19910228

Year of fee payment: 9

Ref country code: DE

Payment date: 19910228

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19910403

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19920208

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19920209

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19920228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19920229

Ref country code: CH

Effective date: 19920229

BERE Be: lapsed

Owner name: ATOCHEM

Effective date: 19920228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19920901

GBPC Gb: european patent ceased through non-payment of renewal fee
NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19921030

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19921103

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

EUG Se: european patent has lapsed

Ref document number: 83400269.3

Effective date: 19920904